TW555746B - Process for manufacturing acrylic acid from propane in the absence of molecular oxygen - Google Patents

Abstract

The invention relates to a process for manufacturing acrylic acid from propane. According to this process, a gas mixture, which is free from molecular oxygen and comprises propane, steam as well as, optionally, an inert gas, is passed over a solid composition of formula (I) Mo1VaTebNbcSidOx, in which: a is between 0.006 and 1, including the end points; b is between 0.006 and 1, including the end points; c is between 0.006 and 1, including the end points; d is between 0 and 3.5, including the end points; and x is the quantity of oxygen bound to the other elements, and depends on their oxidation states, in order to oxidize the propane according to the following redox reaction (1): SOLIDoxidized+PROPANE -> SOLIDreduced+ACRYLIC ACID.

Description

555746 V. Description of the invention (l) " " '" ---- TECHNICAL FIELD The present invention relates to a method for producing acrylic acid from propane in the absence of molecular oxygen. BACKGROUND ART European patent application No. EP_A_6088838 discloses a method for preparing an unsaturated carboxylic acid from an alkane according to a vapor phase catalytic oxidation reaction in the presence of a catalyst, the catalyst containing Mo, V, Te, 〇 = = Emulsions; f is included as the main component and at least one selected from the group consisting of sharp, group, tungsten, titanium, inscription, record, network, benefit, iron, iron, ruthenium, inscription, rhodium, nickel, and , Platinum, = definite: ratio: 疒: and elements in the group consisting of 钸, these elements are compared with 柹: 〇 〇 silicon documents described in the examples of distant documents. And acrylic acid are selective, but they enter Europe in the presence of air: Patent application No. Ερ-Α—8 9 580 9 describes a kind of catalyst of A and oxide, which gas must be ^^ Antimony, and at least one ": including molybdenum, vanadium, niobium, oxygen, tellurium, and / or the conversion of propane to propylene vanadium or aluminum. These catalysts can be used. These catalysts contain the molecule f and are only implemented in For example, each application = limbs such as silicon oxide, although this document manufactures acrylic acid. Only examples 9 and 10 use a silicon oxide-free catalyst to EP + 6 03836 about-one for production and at least one compound-catalyzed 4 yes A complex oxide containing molybdenum, vanadium, tellurium, and oxygen elements, the other elements may be niobium or antimony. Examples of this patent application describe further containing oxidation

Page 6 555746 V. Description of the invention (3) Therefore, the present invention relates to a method for producing acrylic resin by A τ knee P 1, which is characterized by the following order: r * β 丨 丨 7 7 is based on the following reduction reaction (1): solid & + propane-solid reduction + acrylic acid (1) where Moi VaTebNbcSidOx a a between 〇 · 〇06 Between 1 and 1 including the end value; a b between 0 · 0 0 6 and 1 including the end value; a c between 0 · 0〇06 and 1 including the end value; a d between 0 And 3.5, inclusive; and X is the amount of oxygen bonded to other elements, and depends on its oxidation state. ys-This method can achieve acrylic acid selectivity close to 60%. And if by-product propylene and unconverted propane are recovered, the total selectivity can be increased. Other features and advantages of the present invention will become clearer by reading the following description exemplified by the examples. Details of the invention The catalyst used in the present invention satisfies the general formula (丨) described above. = Η 7 of various metals in a mixed oxide composition of the general formula ⑴ as a starting material for the preparation of the composition, and the starting material is not limited to the oxides. Other starting materials:

C: \ 2D-CODE \ 91-05 \ 91104114.ptd 555746 Fifth 'Explanation of invention (4)-Example of acid, halogenated key or example of molybdenum alkoxide-Example of tritium' VC15 ^ V0C13 V0 (0C2H5) 3 -In the case of the hoof-In the sharp example of niobium, niobic acid, ammonium niobium oxide, tartrate, and organic Nb (0-n-Bu) 5 of niobium; and, in general, such as organic and the like. In the son: Pyrexate, molybdenum molybdenum such as MoC15, molybdenum organometallic compounds, such as Mo (〇C2Hs) 5 'molybdenum acetoacetone; in the son: ammonium metavanadate' Or vanadium oxyhalides such as VC14, organometallic compounds of vanadium, such as vanadium alkoxides such as Zizhong · Telluric acid; Zizhong · Niobic acid, Nb2 ((: 204, niobium tartrate, ammonium trioxalate [( NH4) 3 [NbO (C2H4) 3] · 1.5h2〇], ammonium oxalate, niobium or hafnium niobium oxide such as 仳 〇13, NbCls metal compounds, such as niobium alkoxide such as Nb (OC2H5) 5, All the metal salts of compound acids, metal salts of inorganic acids, and metal complexes that can be formed by calcination are generally composed of colloidal silica. I According to a specific example, the formula 豸The solid composition can be mixed by mixing the aqueous solution of sharp acid, heptane! Mesh acid, meta sharp acid and tartaric acid at @ #I. It is preferably mixed with the addition of colloidal silica, and then in the air ^ Pre-calcined at about 3GG ° C and prepared by calcination under nitrogen and large paste (TC). Preferably, in the solid composition of general formula (1) A 0_8 a between 0.5 and 09, inclusive; and -b between 〇.〇4 0.6, inclusive;

555746

-C is between 0.01 and 0.4, inclusive; and-d is between 0.4 and 1.6, inclusive. According to the present invention, acrylic acid can be prepared by passing a gas mixture free of molecular oxygen and containing propylene, water vapor and optionally an inert gas through a solid composition having the general formula (I) as defined above, Complete the redox reaction (1) indicated earlier. Generally, the redox reaction (1) is carried out at a temperature of 200 to 50 ° C, preferably 250 to 450 ° C, and more preferably 350 to 400 ° C. The pressure is generally 1.01 × 10 ~ 4; L0lx 10 ~ 6 Pa ((K1-10 atmospheres) 'preferably 5.05x 10 ~ 5 · 05x 105 Pa (0.5-5 atmospheres / The soil residence time is generally from 0.001 to 900 seconds, preferably from 0.1 to 30 seconds. The volume ratio of propane / water vapor in the gas phase is not limited and can be varied within a wide range. The ratio of the inert gas is also not limited and can be varied within a wide range; the inert gas can be helium, krypton, a mixture of these two gases, or nitrogen, carbon dioxide, etc. For the magnitude of the ratio of the starting mixture, the And the following ratio (volume ratio): propane / inert gas (He-Kr) / H20 (water vapor): 10-20 / 40-50 / 40-5 0 During the redox reaction (1), the solid composition is reduced And gradually lose activity. Therefore, once the solid composition has been at least partially converted into a reduced state, the regeneration of the solid composition can be based on the reaction (2): solid reduction + 〇2-solid dagger (2)

\\ 312 \ 2d-code \ 91-05 \ 91104114.ptd Page 10 555746 V. Description of the invention (7) The following examples are used to describe the present invention, but not to limit the scope of this shoot. " In the formulae of Examples 1 and 2, X is the amount of oxygen bonded to other elements' and depends on its oxidation state. The conversion rate, selectivity and yield are defined as follows: Propane conversion (%) = mole number of propane reacted / mole number of propane added X 1 0 0 Selectivity of propionic acid (% ) = Molar number of acrylic acid formed / Molar number of propane X 1 0 0. Yield of acrylic acid (%) = Molar number of acrylic acid formed / Molar number of propane added X 1 0 0 About The selectivity and yield of other compounds are calculated in a similar manner. Example 1 Preparation of catalyst A of general formula MojQjNbQ nTeQ 22Si] G80x a) Preparation of niobium solution In a 60 ml beaker, 80 g of distilled water was added, and then 6.4 g (0.038 mol) of niobic acid was added. Then 129 g (0.102 mol) of oxalic acid dihydrate was added. Therefore the molar ratio of oxalic acid / niobium is 2. 6 9. Add the solution obtained above to β 0, η \…, and hold the main Du u for 2 hours and 9 minutes while stirring, and cover to prevent volatilization. It can be obtained that 丨 ^ 々 therefore, a 4 丄 π A. J judged a white suspended ocean, cooled it to 30 C with stirring, and left it for about 2 hours. b) Μ, ο, V and D e solution in a 600 ml beaker was added 265 ^ ^ ZbD grams of distilled water, 61 grams (.346 Mo

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Page 12 555746 V. Description of the invention (8) Ear) Gingerbinoide acid '13 .3 g (〇IBTeva, Π.4g ear) Steric acid: supplier / commercial heating the solution obtained above to 60 ° C to maintain i hour 35 eight ± mix, and cover to prevent volatilization. Obtain a knife: while stirring, cool to 30 ℃, and leave it for about 2 hours, and put it in the gerosol solution. It will be 56 g of Ludox dioxide (including 40% by weight of the company) was added to 56 grams of distilled water, and the milk powder was added by DuPont to the stone dioxide; after the liquid was added, 20% of the water was added to the noodles. Preparation of Mo, V, Te, and six liquids. The solution paid remained clear and red. 7 Je each Di then add the previously prepared osmium solution. After a few minutes of mixing, you will get the first orange caramel. The solution was then placed in an oven at 13 ° C overnight. Therefore, 114.9 grams of the precursor in the form of a dried product was recovered, which contained 0.373 mole S1, relative to 22.2% by mass. D) The calcination hole y, 30 grams of the precursor obtained above were pre-calcined at 48.2 ml / min / g of precursor stream at 300 ° C for 4 hours. The resulting solid was then calcined at 600 liters per minute at a solids flow rate of nitrogen at a flow rate of 4 8 · i / min / g for 2 hours. This gave 2 4 · 9 g of catalyst A. Example 2 The general formula Mc ^ Vq 33Nb. ^ Preparation of Teo 22 0x catalyst b The steps were carried out as described in parts a) and b) of Example 1. Sharp solutions were then added to the M0, V, and Te solutions. After searching for a few minutes, a fluorescent orange gel was obtained. Then put the solution into the baking

C: \ 2D-CODE \ 91-05 \ 91104114.ptd 555746 V. Description of the invention (9) Overnight in the box. From this, 88.8 grams of precursors were recovered. Then the steps as described in d) A ^ ^ m, t | ^ J in Example 1 were performed in 4 points, thereby serving 20.8 g of catalyst b. Example 3 Test of Catalyst A ^-5-aJL) -Operation Mode in -ya Pulse Mode The detailed operation mode is as follows. Ancient = an upright reactor, from; loading up: the first-height of 2 = · 46 grams) ^ ^ h 19 mm (sieve openings 1.25 mm) carbon stone particles, the first degree of 5 ml (5.48 g) of catalyst particles with a particle size of 0.5 μm were once similar to the above-mentioned silicon carbide (19.547 g). The reactor was then heated to 250 ° C and the evaporator was heated to 2000 ° C. Power on the pump. Once the reaction has reached the temperature indicated above, the water pump is started and the temperature of the reactor is raised to 350 ° C. The temperature of the reactor was then further increased to μc at a rate of increasing joc at every 10 minutes. The reactor was then stabilized for 30 minutes. Next, oxygen was inputted in 10 pulses, each pulse for 23 seconds, and the catalyst was completely oxidized. When the temperature of the heating point is stable, that is, when there is no longer any exotherm during the reaction (by using a thermocouple placed in the catalyst bed to measure, as the temperature of the catalyst, it may be observed as Μ

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5. Description of the invention (ίο) is a fluctuation in temperature as a function of pulse), it is considered that the catalyst is completely oxidized. The pressure of the reactor into D is about 丨 · 丨 bar, and the pressure through the reactor is reduced by about 0.1 bar. Regarding the actual production of acrylic acid, one redox scheme consists of 60 redox cycles. A redox cycle represents: 13 seconds of propane in a continuous helium-krypton / water stream, -45 seconds of continuous helium-krypton / water stream,-20 seconds of oxygen in a continuous helium-krypton / water stream, -45 Continuous helium-krypton / water flow in seconds. Samples were collected 4 times during the program, each sample representing 1 & cycles. An airbag was also used to collect 4 gas samples, each sample representing about 5 cycles, or the last bag sample only representing 3 or 14 cycles. (The gas samples described were taken during periods corresponding to multiple durations of a cycle so that the theoretical amount of propane injected could be known.) Each wash bottle (25 ml capacity, containing 20 ml of Water) is equipped with a gas + bag 'and when the bottle is connected to the daytime guard of the reactor outlet (just after the liquid is bubbled), the gas bag is opened and the chronograph is started. One cycle lasts i 3 3 seconds, so the duration of the program is 2 hours 丨 3 minutes. In order to check the oxidation state of the catalyst, a new series of 10 oxygen pulses were performed every 23 seconds. It shows that the oxidation state of the solid was maintained during the procedure. For a solid catalyst having a mass-based specific surface area of 10 m2 / g, the number of causes is reduced relative to the surface oxygen reaching 10%.

C: \ 2D-CDDE \ 91 -05 \ 91104114 .ptd Page 15 555746 V. Description of the invention α "" 1 " After the special calibration is completed, the liquid effluent is analyzed by HP 68 90 chromatography. Phase chromatography was used to analyze the gases during the Chrompack's program. Acid titration was performed on the mixture in the bottle at the end of the insert to determine the exact mole number of acid produced during the program and to verify the chromatographic results. A 2) The result was To study the performance of the catalyst over time, a series of tests were carried out for several days under the same conditions. The catalyst underwent 10 tests in a pulsed manner, so that it concluded that the catalyst remained in contact with propane for 130 minutes, and the cumulative time exceeded 6 〇〇pulses. / In a pulse mode program, a series of oxygen pulses of 23 times each time, so that the catalyst can be continuously oxidized. Consider the program reoxidation series and temperature stability. Continue the process, the catalyst stays at 380 ° C for about 40 hours.), T1, T2, T3, 4 and redundant tests according to the above instructions, that is,-divide the 60 cycle program into 4 Part of the 5 cycle.-, = 25 ml of washing and scouring liquid recovered from the second phase of each ship series: Do not. Chromatographic analysis of each bottle. For all recovered effluent C mixture of all 4 bottles) Perform chemical acid titration. 隹 During the entire program, 4 gas samples are analyzed. Milk samples are collected every 15 cycles ^. Therefore, each small wash bottle has _ gas samples'

555746 V. Description of the invention (12) Tables and graphs of the average results of 4 parts (bottle and gas). Programs Bl, B2, B3, B4 and B5 are implemented slightly differently:-throughout the duration of the program, the liquid effluent is recovered into a large 125 ml bottle; the mixture in this bottle is chromatographed And chemical acid titration;-During this procedure, a single 15-cycle gas sample is collected. For these tests, perform a liquid analysis of the entire program and a gas analysis of one part of the program. As a result, the results are not precise enough, which could explain why the carbon balance is poor. For all tests, the result of the chromatographic determination was correct, as the result was determined by chemical titration of the recovered liquid effluent. The results are listed in Table 1 below, where: AA represents acrylic acid; acA represents acetic acid; COX represents carbon oxides; UCF represents a unit conversion factor (or yield).

C: \ 2D-CODE \ 91-05 \ 91104114.ptd Page 17 555746 V. Explanation of the invention (13) Yong Yong ΓΓ rt® w® r ^ · 10 廑, X33 ί 3 Ο ρ α > Full 9 's ^ ✓ s- cheat 3 3H ^ ί5 ankle full / ^ ―V m cheat 3 op 2 ^ r \-3 s 3 ankle Pfir 3 an ankle ㈣ I 3 s ca ^ o " W m bowlM a 荈 c ^ 3 Ό 3 〇 ° 3H 荈 ra ♦ ρί Misc ρ —0's > — bo 1 > ~ Λ ON bo oo to as 〇 \ L〇KJ bo h— ^ LO VO OJ ο I— * I— »vo ON ν〇会 Η— · x] »—fc bo oo Lh > OO yj UJ oo h ~ * vt > J-^ JH _〇 < p > Κ) οο \ 〇-ο a \ 2 〇〇to Ln» — * H — * K) bo h— * L〇VO VO X * —- · 1 > — * »—» Vo H— ^ s H— * Lr > to > 2) 2 ρ ρ a < 4 ^. V 〇1 oo to (— * ON private VT5 K > Co η-— LO OO OJ o Ό 1— v〇b \ ►— * ON bo Ι Ο 2 ^ vo d ρ < 〇Κ) Ό Ο 1— * $ s. ►— * S k > H— ON as bo K) i〇►—- Lk) on K) bo v〇Lr, Ό »— * VO M H— ON Lh KJ d ο 〇 > L as ο — 〇〇— ON 1 oo bo oo sh— * OO Lrt ON Ln Ki! 〇h— »卜 K) v〇h— * OO ON OO Os 5 oo MD XH— * H— ^ v〇OO Lyi w K) ρ ο to · — LO 〇ON > r s. H— * ON OO s bo H— * S ON N3 Co LO oh— * k ) H— * o Ό by VO H— ^ Cj H— * »— * ►— * g (X > W lo ρ ρ > 1— * ΟΝ Κ > ΟΊ —ν〇1 OO OO h— 5 σ \ k) UJ o »— * Lk) to H- ^ VO Lk > Ό Lo X VO Dagger 1—k ON vo oo bo H ~ * H ρ ρ > Κί LO ΟΟ Office ►— * a \ S bo 1— * ON bo ON OO Lk) og UJ ph— * s XH— * 1 H—ks VO o W ο ο · 〇Ν h〇 ^ 0 1 H— ^ OO Ιλ OO H— * H--h—1 ►— * ON UJ H — * 1— ^ LO OS K) VO b〇Ό L〇v〇L〇X > £ o ^ h— »as bo Ό OO h— * ρ ρ > — ^ 3 — ο next to Os ►— * oo u »oo iZ > — * L〇bo CTn LO L〇 • 0's u〇 > — * h—k Ko H— * pl · — ^ ►— X g H— ^ OO H— * 〇, H— * gh— w

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V. Description of the invention (14) 7 The propane pulse is theoretically 10 seconds and actually 13 seconds. Corresponds to the theoretical first value, that is, a 10-second pulse, and the second value listed in parentheses * corresponds to a 3-second pulse. 8 Carbon balance surplus. Since the air bag is porous, it may cause gas analysis errors. 9 Propylene conversion = the sum of UCF. 10 products used: acrylic acid, acetic acid, acrolein, acetaldehyde, acetone and propylene. 11 Determine selectivity by considering the UCF / EUCF of the product.

12 Based on the product formed, calculate the oxygen consumption mole number. " In the redox mode, 'the propane pulse duration (13 seconds) is also taken into account to calculate the yield. It can be seen that the catalyst remained stable throughout the test, while each test gave essentially the same results. The results are very good. The selectivity of acrylic acid (AA) is close to 60% (55% -58% in 10 tests), and the selectivity of propylene (pen) is. The average conversion of propane (Pan) was 17%. In the test. Determined by considering the sum of the U C F of the product.

In addition, the 'decapod' was clean after the catalyst was discharged. That is to say, the phase & which occurred during the standard continuous feed test did not have black deposits at the reactor outlet. b) Continuous feed. These tests are routine, that is, the purpose of the tests is for comparison only. Say it is consistent with the known process. These tests

555746 V. Description of the invention (15) Substitute krypton-helium mixture with air to provide molecular oxygen. Therefore, the feed consists of a mixture of propane, air and water vapor. 1 5 巴。 The pressure at the reactor inlet was about 1.1 5 bar, the pressure through the reactor dropped by about 0.1 5 bar. The weight of the catalyst charged was 4.8 2 g, which was equal to the height of the reactor 5 ml. The results and operating conditions are listed in Table 2 below. Among them: SV means airspeed per hour; AA and acA, 00} (and 110? Have the same meaning as in Table 1.

C: \ 2D-C0DE \ 91-05 \ 91104114.ptd Page 20 555746 V. Description of the invention (16) Table 2 Test Ding 6 Continuous feeding in T7 mode Continuous feeding of propane / air / water (volume) 9.1 / 45.5 / 45.5 9.1 / 45.4 / 45.5 SV (hours 1730 1730 reaction temperature ° c '390 400 hotspot (° c) 408-411 43 1 program duration (hours) after stabilization for 1 hour 30 minutes 1 hour 00 1 hour 00 carbon Equilibrium (%) 105.2 102.4 Propane conversion (%) 9 22.2 3 1.2 Acidity: Chromatographic (Mole) Not determined 52.lx ΙΟ'4 Acidity: Chemical titration (Mole) Not determined 53.8X10 · 4 Acrylic acid ratio (%) 11.0 12.2 Acetic acid ratio (%) 1.0 1.8 Propylene ratio (%) 3.9 3.78 Useful product ratio (%) 16.0 17.88 Cox ratio (%) 6.1 13.34 Selectivity of acrylic acid (%) 49.6 39.0 Selectivity of acetic acid (% ) 4.2 5.8 Selectivity of propylene (%) 17.6 12.1 Selectivity of useful products (%)] 4 72.2 57.2 Selectivity of cox (%) 27.5 42.7 AA amount 15 0.796 0.882 ac A Moore / kg catalyst / hour 0.072 0.194 draw 1_ C: \ 2D-0QDE \ 91-05 \ 91104114.ptd page 21 555746, send Note (17) Propylene conversion = total of UCF. 1 4 pp 'Products used: acrylic acid, acetic acid, acrolein, acetaldehyde, acetone, and propylene. 15 JL · In the redox system, the propane pulse duration is considered Calculate the yield at the same time (13 seconds). By comparing the results in Table 1 (the present invention) and Table 2 (the prior art), it can be seen that in the case of the conversion rate (17-22%), the acrylic acid in pulse mode The selectivity is 8% higher than that of the continuous feed method, and the selectivity of useful products is 10% higher. In the continuous feed method at a higher temperature (right column of Table 2), the conversion of propane 2 is increased, but the choice of acrylic acid Reduced performance, carbon oxide COx straightening Example of test of catalyst B today

As shown above, the amount of carbonized rock (first height) first loaded on the catalyst BI by continuous feeding and pulse method is 2.44 g, the amount of catalytic carbon (first degree) is 5.676 g, and the amount of silicon carbide (The first = 19.617 grams. / Since] The size of the silicon carbide and catalyst particles is the same as in Example 3. In addition, in order to determine whether the propylene produced can be returned to ::: middle-direction propylene Various ratios of propylene were added in place of the recycle station, so 'add to the constant propane flow every 15 cycles according to the following ratio

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555746

C: \ 2D-C0DE \ 91 -05 \ 911041 M.ptd Page 24 555746 V. Description of the invention (20) 3 Table batch S > ^ ^ Ξ 〇〇X S- 杂 's—✓ s: Full w 9 〇 rv ^ W hemp jftjs • Pf8 curtain c ^ 9 4 »v Weng Mang · Bian Yi V FeiΗ— * window 5ε < & 黹 imS- 众 〇 ° O〇's—✓ CO ti a > 3 〇h〇CD K tv > os〇) ¾ 〇 〇 〇as 〇〇 ^ l〇h〇O κ > 1— * ►— * o ro Η— * hemp oj CTs 1 VO ON OO Ό < -〇as o 〇1 〇〇j Ό to ◦ * H oo to to VO i: I— * v〇to N-) Ό I— * ►— »to o ΙΟ NJ 〇〇K > to UJ VO oo VO ON VO ►— * Κί (Ds» — »O to oo 〇» h— ^ l〇oo OJ v〇VO o ►—k to »— * o -J 4 ^ OQ Ον O '% CD tO K > ON 〇〇-P ^ h—k VO H -* OJ VO o »— * VO VO VO > — * to £ 33 * 4vv > — * Lk > Private Lk) v〇1 OJ OO L〇o I -— * 0 1 o L〇-P ^ NJ 〇— -4 ^ 5 (— oo —J oo ►— * t-r > NJ h〇VO 0's 〇 > > — »o ΙΟ Ki VO oo 〇 > NJ Ό 〇 > Ό 1-k -P ^ ►-* o OJ bO to ON ON K > Ό Cn Lk > VO as o to S 4 ^ Wp 〇〇f 卜 v ►— * oo t-Λ? Oo ON I—k to v〇LO o to fO ov〇o κ > OJ 今 iJife LO to LO 1 LO K5 CTn-^ J LO to o 0 1 o K) ο Κ ^ \ On O bo a \ ^ 0 1— »to oo to public L〇Lk) oo v〇o-^ J a \ v〇On Ν · >-ro On to 〇 > * -— »ON VO ro oo UJ i ^ ri V〇tn 〇 • &1; 1 ro H—fc 〇OJ oo to CTN Ln NJ ^ tk UJ NO K) to ih« p C: \ 2D-CODH \ 91- 05 \ 91104114.ptd Page 25 555746 V. Description of the invention (21) 17 Useful products: acrylic acid, acetic acid, acrolein, acetaldehyde, acetone and acrylic. 18 In the redox mode, the propane pulse duration (13 seconds) is also taken into account to calculate the yield. 19 Add propylene flow to constant propane flow every 15 cycles according to the following ratio: 100% propane-0% propylene, 15% cycle 100% propane-10% propylene, 15 cycles Cycle 10% propane-20% propylene, every 15 cycles 100% propane-34% propylene, every 15 cycles So regardless of the reaction temperature (3 2 0 ° C, 3 4 0 ° C or 3 6 0 ° C ) How, all added acrylics are transformed. The propylene produced is therefore considered to be a product, not a reactant.

C: \ 2D-CODE \ 91-O5 \ 9n04114.ptd page 26 555746 Schematic description C: \ 2D-CODE \ 91-05 \ 91104114.ptd page 27

Claims (1)

Repair iL Say 4.1 · 555746., 91104114 Six ------- ^ VSi * 4 · 1 ^ 5 «4 1 · A method for producing acrylic acid from propane burning, where n: | r ^ r ^ # and contains propane, water vapor, and Optionally, a gas-filled compound of an inert gas is passed through a solid composition having the following general formula (I): M〇1VaTebNbcSidOx (I) where: a is between 0.06 and 1, inclusive -B is between 0.06 and 1, including the end value; c is between 0.006 and 1, including the end value; d is between 0 and 3.5, including Extreme values; and X is the amount of oxygen bonded to other elements, and depends on its oxidation state; 〆, 俾 oxidizes propane according to the following redox reaction (1): solid oxidation + propane-solid reduction + Acrylic acid (1) 0 2 · The method according to item 1 of the scope of patent application, wherein, in the solid composition of the general formula (丨):-a is between 0.09 and 0.8, including End value;-b is between 0.04 and 0.6, including the end value;-c is between 0.01 and 0.4, including the end value; and-d is between 0 · 4 and 1 Between 6, including end value. 3. The method according to item 1 or 2 of the scope of patent application, wherein the redox reaction (1) is carried out at a temperature of 2000-500 ° C. 4. The method according to item 1 of the scope of patent application, wherein the redox reaction (1) is carried out at a temperature of 250-450 ° C. 5. The method according to item 1 of the scope of patent application, wherein the redox reaction \\ A326 \ Patent case file \ 91 \ 91104114 \ 91104114 (replacement) -l.ptc page 28 555746 (1) It should be carried out under a pressure of 1 · 01 x 1 04 ~ 1 · 01 X 106 Pa (0 ·: 1 -10 atmospheres). 6. The method according to item 1 of the scope of patent application, wherein the redox reaction (1) is under a pressure of 5.05 X 1〇4 ~ 5 · 〇5 X 1〇5 Pa (〇 · 5-5 atmospheric pressure) get on. 7. The method according to item 1 of the scope of patent application, wherein the redox reaction (1) is carried out at a residence time of 0. 001 to 90 seconds. 8. The method according to item 1 of the scope of patent application, wherein the redox reaction (1) is carried out at a residence time of 0 · 1-30 seconds. 9 · The method according to item 1 of the scope of patent application, wherein the method is performed when the number of reasons for the solid composition is between 10% and 40%. 10. The method according to item 1 of the scope of patent application, wherein, once the solid composition has been at least partially converted into a reduced state, the regeneration of the solid composition will be based on the reaction (2):, solid reduction + 〇2-solid gas (2) is carried out in the presence of oxygen or an oxygen-containing gas at a temperature of 250-500 ° C by heating over the time required for reoxidation of the solid composition. 11. The method according to item 10 of the scope of patent application, wherein the redox reaction (1) and regeneration are performed in a two-stage device, that is, a reactor and a regenerator that are operated at the same time, in which two batches of solids are combined Things alternate periodically. ^ 1 2. The method according to item 10 of the patent application range, wherein the redox reaction (1) and regeneration are performed in the same reactor by changing the reaction and regeneration period. 匸: \ Patent Master File \ 91 \ 91104] 14 \ 91] 04114 (Replacement) -1. 口 【(: Page 29 555746 6. Scope of patent application 1 3. The method according to item 10 of the patent application scope, wherein the redox reaction (1) and regeneration are performed in a transfer bed reactor. 14 · The method according to item 1 of the scope of patent application, wherein the propylene and / or unreacted propane produced are recovered to the inlet of the reactor. 15 · The method according to item 1 or 2 of the scope of patent application, wherein the oxidation reduction reaction (1) is performed at a temperature of 250-450 ° C. 16 · The method according to item 1 or 2 of the scope of patent application, wherein the oxidation reduction reaction (1) is performed under a pressure of 5.005 x 104 to 5.05 x 1 05 Pa (0.5_5 atm). 17. The method according to item 1 or 2 of the scope of patent application, wherein the oxidation reduction reaction (1) is carried out at a residence time of 0 · 1-30 seconds. 18. The method according to item 10 of the scope of patent application, wherein the generated propylene and / or unreacted propylene is recovered to the inlet of the reactor. \ \ A326 \ Patent case file \ 91 \ 91104114 \ 91104114 (replace μ 1. Ptc page 30